Anodes with corner and edge modified designs

ABSTRACT

Porous sintered anode bodies for capacitors formed from valve metals are treated by electrolysis to form a dielectric layer and coated with cathode layers. When standard parallelepiped shapes are used, cathode coverage at the edges and corners is non-uniform and failures occur at those locations. Rectangular prisms, obround prisms and cylindrical prisms are formed with transition surfaces at edges and corners, such as chamfers and curves, to enhance cathode layer uniformity. The transition surface greatly enhances the application of polymer slurries.

FIELD OF THE INVENTION

This invention relates to optimized geometries for anodes in solidelectrolytic capacitors. More particularly, the invention relates tomodifications to the geometries of capacitor anodes to facilitatecoating of the total surface with a conductive polymer and avoiduncoated areas where surfaces meet.

A rectangular prism-shaped anode with rounded, chamfered, or cut outcorners allows for improved coating of the corners and transitionsurfaces by cathode layers in an electrolytic capacitor. Edgelessrectangular, cylindrical, elliptical or obround anodes allow forimproved coverage and reduced stress on the anode. More particular, thepresent invention allows corners or edges to be covered by cathodelayers applied by dipping the anode into a liquid slurry or suspensionof the cathode material followed by a drying or curing step, savingprocessing steps. The present invention also provides a means ofreducing mechanical stress on the edges of cylindrical anodes used inhermetically sealed solid electrolytic capacitors.

BACKGROUND OF THE INVENTION

The anode of a typical solid electrolytic capacitor consists of a porousanode body with a lead wire extending beyond the anode body andconnected to the positive mounting termination of the capacitor. Theanode is formed by first pressing a valve metal powder into a pellet.Alternatively, the anode may be an etched foil, for example aluminumfoil as is commonly used in the industry. Valve metals include Al, Ta,Nb, Ti, Zr, Hf, W, and mixtures, alloys, nitrides, or sub oxides ofthese metals. NbO may also be used as an equivalent to a valve metal.The pressed anode is sintered to form fused connections between theindividual powder particles. All anodes are anodized to a pre-determinedvoltage in a liquid electrolyte to form an oxide of the valve metalwhich serves as the dielectric of a solid electrolytic capacitor. Aprimary cathode material, such as a conductive polymer or manganesedioxide, is subsequently applied via a multi-cycle liquid dippingprocess. In order to minimize the equivalent series resistance (ESR) ofsolid electrolytic capacitors the devices subsequently are dipped in asilver paint, which when dried provides a highly conductive cathodeterminal coating. A carbon layer, usually applied between the primarycathode material and terminal silver layer, serves as a chemical barrierto isolate the two layers. The silvered anodes are then assembled andencapsulated to form the finished devices. The encapsulation process maybe a transfer molding process or conformal coating process tomanufacture surface mount capacitors. Conformal coating with a plasticsealant is often used to manufacture leaded devices. The industrystandard case sizes for surface mount capacitors are rectangular solids,thus rectangular anodes or parallopipeds are used in these devices tomaximize volumetric efficiency. In hermetically sealed capacitors thesilvered anodes are placed in cylindrical cans containing a solder plug.Heat is applied to the can to reflow the solder. After reflow the soldersecures the anode in place and forms an electrical connection betweenthe cathode and the metallic can. The anodes used in these devices arecylindrical.

The reliability of all such devices is highly dependent on the qualityof the external cathode layers.

The ability to isolate flaws in the dielectric is a requirement of theprimary cathode material chosen for manufacturing solid electrolyticcapacitors. This property of the primary cathode material results from aprocess termed ‘healing’. The application of voltage to the capacitorcauses current to flow through flaw sites in the dielectric, resultingin an increase in the temperature at the defect site due to Jouleheating. As current flows through the flaw site the counter electrodematerial immediately adjacent to the flaw site is renderednonconductive. The temperature of the cathode layer immediately adjacentto the flaw site also increases due to conduction. When manganesedioxide is employed as the cathode material, the manganese dioxideimmediately adjacent to the flaw site is converted to manganesesesquioxide at the decomposition temperature of manganese dioxide(500-600° C.), thus isolating the flaw. Since the resistivity ofmanganese sesquioxide is several orders of magnitude greater than thatof manganese dioxide, leakage currents through the flaw sites decreaseaccording to Ohm's law. A similar mechanism is postulated for conductivepolymer counter electrodes. Possible mechanisms to account for thehealing mechanism of conductive polymer films include completedecomposition of the polymer adjacent to the flaw site, over oxidationof the polymer, and dedoping of the polymer at the flaw site. Attemperatures above 600° C. the amorphous tantalum pentoxide which servesas the dielectric in tantalum capacitors is converted to a conductivecrystalline state. Thus, in order to be an effective primary cathodematerial for tantalum the material must convert to a nonconductive stateat temperatures below 600° C. The maximum withstanding temperatures ofother valve metal oxides is similar to that of tantalum.

Since the graphite and silver layers do not decompose to formnonconductive materials at temperatures below 600° C., continuouscoating of all dielectric surfaces by the primary cathode material isessential to prevent the graphite or silver layers from contacting thedielectric. If the graphite or silver do contact of the dielectric thedevice there will be a short circuit.

Conductive polymer coatings are applied to the anode using a variety ofmethods as described in U.S. Pat. No. 6,072,694. The use of polymerslurries or liquid suspensions containing pre-polymerized conductivepolymer as an alternative to the monomer is very attractive due to thesimplicity of manufacturing, the reduction in waste, and the eliminationof costly and time consuming washing steps after each coating step asdirected in U.S. Pat. No. 6,391,379. Although this process approach isattractive it has not yet been implemented on a production scale. One ofthe principle technical obstacles to the successful implementation of apolymer slurry to serve as the primary cathode layer is the difficultycoating edges and corners of the anode with slurry. These materials tendto pull away from corners and edges due to surface energy effects. Theresulting thin coverage at corner and edges results in reducedreliability of the device. The magnitude of the force pulling the liquidaway from the edge is given by the Young and Laplace Equation:

Δp=γ/r

Wherein

Δp=the pressure difference causing the liquid or slurry to recede froman edge

γ=the surface tension of the liquid or slurry; and

r=the radius of curvature of the edge.

This effect is illustrated in FIG. 1.

During dipping the liquid phase of a suspension will enter the pores ofthe anode. If the particles in the suspension are larger than the pores,they will be prevented from entering the anode body and can buildup onthe external surface of the anode. Thus external buildup on the facesand corners of the anode after dipping in the slurry is somewhatdependent on the void volume (i.e. density) of the anode. Variations inlocal density of the anode can result in non-uniform coating, especiallyon the corners and edges of an anode.

The reliability of a solid electrolytic capacitor is also degraded dueto differences in coefficients of thermal expansion between the anodebodies and encapsulates material. These mismatches lead tothermo-mechanical stresses on the anode/dielectric during surfacemounting. These stresses are greatest at the edges and corners of theanode body. Capacitor manufacturers rely on the external cathodecoatings of carbon and silver paint to reduce or distribute the stress,especially at high stress points like corners and edges of the anode.However, the external cathode layers often are applied in the form ofliquid slurries or suspensions which produce thin coverage at cornersand edges resulting in reduced reliability of the device.

Capacitor manufacturers have also employed rectangular prism anodedesigns with designated rounded or chamfered edges in order to reducethe thermo-mechanical stress on edges of surface mount devices afterencapsulation. An anode with chamfered edges at the top of the anode wasdescribed by D. M. Edson and J. B. Fortin in a paper published in theCapacitor and Resistor Symposium in March 1994 entitled “ImprovingThermal Shock Resistance of Surface Mount Tantalum Capacitors.” Theseauthors used finite element analysis and failure site identificationtechniques to demonstrate that most failures which occurred duringsurface mounting were along the top edges of the anode (surface wherethe lead projects). A modified anode design as depicted in FIG. 2 wasreported to reduce the surface mount failure rate.

An anode with a chamfered portion at the top edge of the anode (see FIG.3) is described in U.S. Pat. No. 5,959,831 (Maeda, et al.). Thepurported purpose of this design is to reduce the likelihood of theprimary cathode layer wicking up the anode lead wire during dipping. InU.S. Pat. No. 7,190,572 the inventor claims that excess edge buildup ofmanganese dioxide can be avoided by chamfering the bottom edges of theanode (see FIG. 4). The buildup of manganese dioxide at the corners isthe opposite phenomenon to that observed when conductive polymers areapplied. Also, some rounding of side edges of pressed anodes has beenobserved in capacitors on the market. (see FIG. 5).

One of the drawbacks of rounded side edges as depicted in FIG. 5 is thedifficulty in pressing reproducible anodes with these geometries using aradial press design. A radial press design is defined as a press whichcompacts the powder in a direction perpendicular to the anode lead wire(typically the long axis of the compact). Axial presses are defined as apress which compacts the powder in a direction parallel to the anodelead wire. Although axial pressing allows for greater flexibility inanode geometries of interest to capacitor manufacturers, it often leadsto other problems such as smearing of the powder at the surface as itslides inside the die cavity and density gradients in the anode in theaxial direction of the anode lead. The high density regions and powdersmearing make it more difficult for the liquid phase of a slurry orsuspension to enter the pores of the anode, exacerbating the problems ofpoor cathode coverage. Although powder smearing and density gradientsalso occur with radial pressing, they occur to a considerably lesserdegree since the longest dimension of the anode is typically along thelength of the anode lead wire.

Although rounded and chamfered edge rectangular anodes have beendescribed and utilized in the industry for years, the concept of cornerchamfering has not been explored. In fact, since the edges represent aline drawn between two points, the corners, corner rounding would not beexpected to provide benefits beyond that of edge rounding. However,analysis of many electrically failed conductive polymer anodes indicatesthat the dielectric breakdown mainly occurs on the corners of theanodes, as shown in FIG. 6.

Another approach to improving corner coverage would be to eliminate thecorners through the use of cylindrical or obround anode geometries.However cylindrical anodes are volumetrically inefficient when used inindustry standard case dimensions for surface mount product. Obroundanodes are more volumetric efficient, but pressing these anodes isgenerally done on an axial style press. This leads to density gradientsand high densities at either the top or bottom edge of the anode. Thesehigh density edges are as difficult to fully coat with a slurry as acorner on a rectangular shaped anode.

Axial leaded hermetically sealed solid electrolytic capacitors areextremely reliable capacitors. Because the only heat introduced in thesolder attach process is to the leads, on the opposite side of theprinted circuit board (PCB) as the part, the temperature rise is small,and damaging forces (mismatch in coefficients of thermal expansion)created by this process are minimal. Compared to the forces created inthe solder process for surface mount capacitors (SMT) where the entirecapacitor package is immersed into the high thermal profile of thesolder, theses forces should never create failures. This fact is bornout in the recommended applications of these capacitors. Leadedcapacitors may be used up to 80% of its nameplate voltage, whereas theproduct is limited to 50% of its nameplate voltage.

The big disadvantage for these leaded products is the susceptibility tomechanical forces created in handling of the parts. As loose pieces arehandled, there is a potential of dropping the device, crimping thedevice, or pressing on the device in the process of moving from packageto place in circuit that is not detectable. If the piece survives theinitial electrical testing, the flaw created by the physical force cangrow and become a circuit failure at a later point.

Through diligent research the present inventors have found that polymercoverage and leakage are improved by various techniques of modifying thecorners of anodes to improve the corner coverage with the primarycathode material. Problems of poor edge coverage on obround orcylindrical anodes can be overcome by modifying the edges of these anodedesigns. The reliability of hermetically sealed devices can be improvedby similarly modifying the edges of cylindrical anodes used in thisstyle capacitor.

SUMMARY OF THE INVENTION

It is an object of the present invention to provide anode designs whichfacilitate corner and edge coverage by the cathode layers, especiallythe primary cathode layer.

It is another object of this invention to provide anode designs withmodified corner geometries which are readily pressed using conventionalradial presses.

Another object of this invention is to achieve corner rounding withminimal loss of anode volume.

It is yet another object of this invention to provide anode designssuitable for use with conductive polymer slurries.

Yet another object of this invention is to provide anode designs withimproved leakage characteristics relative to conventional anodes.

These and other advantages are provided in anodes with modified edge andcorner geometrics through the use of transition surfaces such as roundedor chamfered corners and edges and by an anode with a groove cut in eachcorner of the anode.

Yet another embodiment of the present invention is provided by acylindrical or obround anode with grooves cut along either the top orbottom edge, by an edgeless rectangular anode, by an edgeless obroundanode, and by an edgeless cylindrical anode.

DESCRIPTION OF DRAWINGS

FIG. 1 is an illustration of a liquid receding from an edge due tosurface tension effects.

FIG. 2 is a depiction of prior art top edge chamfered anode.

FIG. 3 is a depiction of prior art top edge chamfered anode.

FIG. 4 is a depiction of prior art bottom edge chamfered anode.

FIG. 5 is a cross sectional view of prior art rounded side anode.

FIG. 6A and FIG. 6B indicate the failure site location of anodesfollowing a breakdown voltage test.

FIG. 7 is a depiction of a corner chamfer anode design.

FIG. 8 is a depiction of an edgeless rectangular anode.

FIG. 9 is a depiction of an edgeless obround anode.

FIG. 10 is a depiction of an edgeless cylindrical anode.

FIG. 11 depicts the mechanical forces acting on a hermetically sealeddevice.

FIG. 12 depicts edge rounding of cylindrical anode in hermeticallysealed construction.

FIG. 13 depicts a rectangular prism for illustration of surfaces, edgesand corners.

FIG. 14 depicts a rectangular prism in perspective view.

FIG. 15 is a depiction of a corner cut anode design

FIG. 16 depicts polymer coverage of corner cut anodes

FIG. 17 depicts polymer coverage of conventional anode with dielectricshow through evident at corners due to incomplete polymer coverage.

FIG. 18 plots leakage for standard and corner cut anodes

FIG. 19 depicts polymer coverage on anodes with rounded corners.

FIG. 20 depicts polymer coverage on anodes with conventional corners

FIG. 21 depicts polymer coverage at the top of an obround anode pressedon an axial press.

FIG. 22 depicts polymer coverage at the bottom of an obround anodepressed on an axial press.

DETAILED DESCRIPTION OF THE INVENTION

A porous pellet is prepared by pressing a powder and sintering to form aporous body. The pellets may be made from any suitable material such astantalum, aluminum, niobium, hafnium, zirconium, titanium, or alloys ofthese elements, nitrides and suboxides. Tantalum and ceramic niobiumoxide are the preferred materials. Tantalum is the most preferredmaterial. The sintered pellet is then anodized to form the oxide filmwhich serves as the dielectric of the capacitor. The internal surfacesof the anodic oxide film are next coated with a primary cathode layer.Manganese dioxide may be applied as a primary cathode layer by dippingin manganous nitrate solution and converting the nitrate to manganesedioxide via heating in a pyrolysis oven. Typically the conversion stepis carried out between 250° and 300° C. Alternatively, an intrinsicallyconductive polymer can be employed as the primary cathode layer. Theconductive polymer material is typically applied as a monomer usingeither a chemical oxidative process or by dipping in a preformed polymerslurry. In the case of a chemical oxidative process, byproducts of thereaction are removed by washing and typically multiple dips and washingsare required prior to a reanodization process used to isolate the defectsites in the dielectric. The pellets are then placed in suitableelectrolyte bath, for instance a dilute aqueous phosphoric acid solutionwith a conductivity in the range 50 to 4000 micoS/cm. Voltage is appliedto drive the process which causes isolation of the dielectric flaw sitesThis process may not be required in the case of application of theconductive material by dipping the anodes in a preformed(prepolymerized) polymer slurry. The process is repeated to insurecomplete coverage of the internal and external dielectric surfaces. Thecomponents are subsequently dipped in a carbon suspension to coat theexternal surfaces of the primary cathode material. A silver layer isformed by dipping the device in a silver paint to form an externalcoating.

FIG. 1 depicts the manner in which a liquid or slurry pulls away from anedge or corner due to surface tension effects. FIG. 2 depicts prior artin which the top edges of a surface mount capacitor were chamfered toreduce stress on those edges. FIG. 3 is a depiction of an anode withchamfered top edges as described in U.S. Pat. No. 5,959,831 (Maeda, etal.). FIG. 4 depicts chamfering of bottom edges as depicted in US2005/0231895 A1. FIG. 5 is a picture of a commercial capacitor which hasbeen cross sectioned to reveal rounded edges. FIG. 6 is a picture ofcapacitors following a breakdown test indicating the failures occurredon the corners of the anode. In a breakdown voltage test, a powersupply, resistor, fuse, and capacitor are placed in series. The voltageapplied to the capacitor is increased until the capacitor breaks down asindicated by the blown fuse. Especially in the case of capacitors withpolymer slurry cathode the failure site occurs predominantly on thecorners of the anode which are poorly coated by the polymer slurry.

For purposes of understanding the invention, reference is made to FIG.13. FIG. 13 shows a rectangular prism or a parallelopiped. The X, Y, andZ axes are defined with respect to origin “O.” The exposed surfaces arelabeled XY, XZ, and YZ. An edge is defined as the intersection of twosurfaces. A corner (or point) is defined as the intersection of threesurfaces or three edges.

Modification of an edge can be defined by reference to FIG. 14. FIG. 14represents an anode in perspective view. A surface XZ with a length X′and width Z′ represents a first external surface of an anode. A surfaceYZ with a length Y′ and width Z′ represents a second external surface ofan anode. For conventional anodes XZ and YZ meet to form a right angleat an edge. In an edge modified design the first surface XZ will deviateat point a and distance X″ from the edge, e, which is the projectedintersection of XZ and YZ. The second surface of the anode will deviatefrom YZ at point b and distance Y″ from e. This deviation creates atleast one additional surface, herein defined as a transition surface,TS. In one embodiment the deviation is a straight diagonal line betweenpoints a and b wherein the transition surface creates a chamfer. Inanother embodiment the transition surface is a non-linear, curved, orradiused edge. Edge modified designs as defined here refers to anydeviation of the external surface from XZ and YZ such that:

0.03 mm<X″<0.5X′

and

0.03 mm<Y″<0.5Y′.

The concept can be extended to a third dimension of a conventionalrectangular prism. A corner, c, is defined by the projected intersectionof three surfaces YZ, XZ and XY. The surface XZ with a length X′ andwidth Z′ representing an external surface of an anode. In a cornermodified design the surface XZ will also deviate at point d and distanceZ″ from c. A corner modified design as defined herein refers to anydeviation of the external surfaces such that:

0.03 mm<X″<0.5X′

and

0.03 mm<Y″<0.5Y′

and

0.03 mm<Z″<0.5Z′.

In a conventional SMT the anode shape is a regular rectangular prism asillustrated in FIG. 13. The surfaces all intersect at right angles (orapproximations thereof), providing six surfaces and twelve edges.

According to this invention, most or all of the edges are modified toform transition surfaces. The transitions may be flat as in atraditional chamfer or bevel. Alternately, the transition may formmultiple chamfers including, in the limit, a curved surface such aswould be obtained using a corner round router bit.

When rounded edges intersect, a quarter of a hemisphere is formed whichmaybe regular, as when all radii of generation are equal or compoundwhen the radii of the generating curves differ.

Referring again to FIG. 14, it is apparent that the size of a straightbevel or chamfer can be defined in terms of X″, Y″, and/or Z″. Sincethere are twelve edges and eight corners formed by six surfaces, a greatvariety of shapes can be formed when the lengths X, Y and Z differ fromeach other or when different edges are chamfered or when only cornersare chamfered. Depending upon the size of the anode-case size-differenttransition surface shapes and sizes are found to be preferred.

As a first example of a body having a transition surface, reference ismade to FIG. 7. Anode body 71, having six planar sides 73, 74, 75, 76,77, and 78 and an anode lead 79 has been chamfered at each corner toprovide transitional planar surfaces 81, 82, 83, 84, 85, 86, 87, and 88.This shape directly addresses the problem with corner coating asillustrated in FIG. 6A and FIG. 6B. This is a corner chamfer anode.

When edges and corners are all curved, the result is an edgeless shapeas shown in FIG. 8. Three transitional surfaces are present, a shortside curved transitioned surface 91, a long side curved transitionalsurface 93 and a corner quarter hemisphere 95. In the preferredembodiment, all radii of generation are equal but such is not necessary.For small case sizes a greater radius in the Z direction may bepreferred.

When the curvature at the edges in the YZ surface is expanded to becomea continuous curve, the resultant figure is an obround prism as shown inFIG. 9. The YZ surface has been replaced with a curved surface, such assemicircular in cross-section. In the preferred embodiment, thetransition surfaces form the XY surface and from the semicircular sideare radiused into the XZ surface (cf. 103) and the transition surfacefrom the XY surface (cf. 105) are radiused into the XZ surface. Such ananode has no sharp edges save for some flashing at the points ofjuncture of the dice employed. The XY surface of an oblong prism may beflat or curved.

Extrapolation of the edgeless obround shape of FIG. 9 is the edgelesscylinder of FIG. 10. A cylindrical anode has traditional round sides107, but the transition surface 111 to the flat top 109 (and bottom, notshown) is chamfered or, in the drawing, rounded or curved to make asmooth transition from side to top.

When the basic prism shape is obround, the edges and corners may haveconsistent or changing radii, but the chord for the curve is definedusing the same criteria as for a chamfered surface. When the figure is acylinder, the radius of the circle of origin becomes one length, and theheight of the cylinder becomes the other length, i.e., the intersectionof planar surface and circumferential surface is characterized as 0.03mm<R<r and 0.03 mm<H<h/2 where r and h are the radius of the circle oforigination and H the height of the cylinder.

The edgeless cylinder has particular application in hermetically sealedleaded devices.

Failure site analysis reveals that the vast majority of failures, up to95%, will appear on the edges of the cylindrical anode. These edges aremost susceptible to any outside forces applied to the case wall (FIG.11). In between these edges, the pellet structure offers a strongresistive structure that will spread the force and absorb it. In betweenthe edge and the sealed, top of the case, the case can compress toabsorb the force. At the edges, the forces can create a fracturing forceon the pellet. The relative stresses are in the order S¹, <S², <S³. Thetop edge (nearest the anode seal) is more susceptible than the bottomedge (nearest the cathode lead) as the closed end of the barrel addsstiffness here.

In order to mitigate this failure mechanism the edges of the pellet canbe rounded. By eliminating the sharp edge (FIG. 12), the amount of forcerequired to fracture or chip the pellet increases tremendously. Once thepellet is soldered in the case, the sharp edges would have beeneliminated and replaced with a tapering solder thickness. The radiusedor rounded elements nearest the outer diameter have capabilities ofspreading blunt forces through the case. The radiused elements furthestfrom the outer diameter have thicker solder which creates additionalbuffering.

It has been found that a second approach to enhancing coverage issurprisingly effective. An anode having cut-away portions at thecorners—hereinafter a corner cut anode—is effective in collectingconductive polymer at the corners during the coating process. FIG. 15shows a preferred corner cut anode sintered body. At the juncture ofthree surfaces 73, 75 and 78, two cuts are made to create two additionaltransitional surfaces, 121 and 123. This pattern is repeated at theother seven corners to form “pockets.” The improvement may be seen inFIG. 16 when contrasted with FIG. 6 and FIG. 17. While not being boundby any theory, it is seemed that monomer, and subsequently polymer,accumulates on the surfaces of the transition surface 121, 123 andcompensates for the thin or incomplete layers found in standardrectangular parallelepiped shape for anodes. The corner cut anode seemsparticularly suitable for dipping in polymer slurries.

Polymer slurries of intrinsically conductive polymers are an alternativecoating methodology to the formation of polymer from a monomer andcatalyst on the surface of the oxidized pellet. Slurries may be appliedusing a cross-linking agent as disclosed in U.S. Pat. No. 6,451,074. Theuse of slurries reduces the number of coating steps when making thecapacitor and reduces the loss of monomer due to contamination. U.S.Published Application No. 2006/02336531 discloses polythiopheneparticles with filler as a coating material of conductive polymer. Anyintrinsically conductive polymer may be used. Polyaniline is preferreddue to ease of handling. Coating thickness should be at least 0.25micrometers, preferably at least 1 micrometer and optimally at least 3micrometers to obtain complete coverage of all edges. The use of anodepellets with transition surfaces at the end and/or sides away from theanode lead allows reliable mechanical dipping into the slurry withminimal deposition of polymer on the anode lead. The capacitor precursorthen may be coated with graphite and Ag, a cathode lead attached andfinal assembly performed.

A fluted anode is one which has surfaces which are not substantiallyflat. The variations in the surface may be, but are not necessarilysymmetrical or repeated in a pattern. Examples of fluted anodes may befound in U.S. Pat. Nos. 7,154,742; 7,116,548; 6,191,936; and, 5,949,639.The capacitors disclosed in these references are pressed to havesubstantially flat ends where anode lead projects and at the oppositeend. Most have flat sides except for the penetrations into the body ofthe anode. Multiple sharp edges are present and present challenges whencoatings are applied.

Modifications of the external surfaces to remove sharp angles results inimproved coating. The edges and/or corners may be chamfered or curved inthe manner of FIGS. 7 and 8 to achieve a more uniform coating of thepolymer. Triangular corners as shown in FIG. 7 and notched corners suchas shown in FIG. 15 are also preferred. Internal surfaces, meaning thosewholly within the interstices of the flutes need not be modified. Inpreferred embodiments, multiple flat wires are used as anode leads.

Example 1

Commercial electronic grade 22,000 CV/g tantalum powder was pressed toform anodes to a density of 5.5 g/cc with dimensions 4.70×3.25×1.68 mmusing a radial action press. The punches of the press were modified tocreate a notch or v-cut in each corner of the anode as depicted in FIG.15. This modification to the corners is referred to as corner cut anodedesigns. The sintered anodes were anodized at 100 volts in an aqueousphosphoric acid electrolyte maintained at 80° C. The parts weresubsequently dipped in liquid suspensions containing pre-polymerizedpolyethelyenedioxthiophene (PEDT). Photomicrographs were taken todetermine the degree of polymer coverage on the corners of the anodes(FIG. 16). After application of a conductive polymer slurry the partswere dipped in a carbon suspension used for commercial tantalumconductive polymer capacitors. The anodes were dipped in an electronicsgrade silver paint prior to assembly and encapsulation to form surfacemount tantalum capacitors. After encapsulation 25 volts was applied tothe capacitors and leakage was read through a 1 k ohm resistor afterallowing 60 seconds for the capacitors to charge. The results wereplotted in FIG. 17.

Comparative Example 1

Commercial electronic grade 13,000 CV/g tantalum powder was pressed to adensity of 5.5 g/cc with dimensions 4.70×3.25×1.70 mm using a radialaction press. Conventional punches were used which created well definedcorners typical of anodes used in the industry. The sintered anodes wereanodized to 130 volts in an aqueous phosphoric acid electrolytemaintained at 80° C. The parts were subsequently dipped in liquidsuspensions containing pre-polymerized polyethelyenedioxthiophene(PEDT). Photomicrographs were taken to determine the degree of polymercoverage on the corners of the anodes (FIG. 18). After application ofthe conductive polymer slurry the parts were dipped in a carbonsuspension used for commercial tantalum conductive polymer capacitors.The anodes were dipped in an electronics grade silver paint prior toassembly and encapsulation to form surface mount tantalum capacitors.After encapsulation 25 volts was applied to the capacitors and leakagewas read through a 1 k ohm resistor after allowing 60 seconds for thecapacitors to charge. The results and comparison were plotted in FIG. 18wherein DCL is direct current leakage and PE is post-encapsulation. Acomparison of the polymer coverage and leakage distributions afterencapsulation demonstrates the improvements obtained with the corner cutanode design relative to prior art.

Example 2

Commercial electronic grade 13,000 CV/g tantalum powder was pressed to adensity of 5.5 g/cc with dimensions 4.57×3.10×1.63 mm using a pill stylepress. The lead wire is attached after pressing with this type of press.The action of this style press generates anodes with rounded corners onone side of the anode. The corners on the opposite side of the anode aresharp, well defined corners. The sintered anodes were anodized to 130volts in an aqueous phosphoric acid electrolyte maintained at 80° C. Theparts were subsequently dipped in liquid suspensions containingpre-polymerized polyethelyenedioxthiophene (PEDT). Photomicrographs weretaken to determine the degree of polymer coverage on the rounded cornersof the anodes (FIG. 18). Photomicrographs taken of the opposite side ofthe anode demonstrates the poor polymer coverage on the sharp welldefined corners of the anode (FIG. 19). These pictures clearly indicatethe need to modify the corners of the anodes in order to obtainsufficient coverage using slurries or suspensions to apply cathodelayers.

Comparative Example 2

In order to eliminate the corners completely an axial press was used topress obround anodes. Commercial electronic grade 22,000 CV/g tantalumpowder was pressed to an average density of 5.5 g/cc with dimensions4.70×3.25×0.81 mm. An obround shaped die was used to press an anodewithout corners. The sintered anodes were anodized to 100 volts in anaqueous phosphoric acid electrolyte maintained at 80° C. The parts weresubsequently dipped in liquid suspensions containing pre-polymerizedpolyethelyenedioxthiophene (PEDT). Photomicrographs were taken todetermine the degree of polymer coverage on the anodes. Polymer coverageat the top of the anode, where the density was less than 5.5 wasacceptable (FIG. 20). However, at the bottom of the anode where thepress density was greater than 5.5 the edges of the anode were notcovered with polymer (FIG. 21). The density gradient observed in theseanodes is characteristic of anodes produced on an axial press.

The invention has been disclosed in regard to preferred examples andembodiments which do not limit the scope of the invention disclosed.Modifications apparent to those with skill in the art are subsumedwithin the scope and spirit of the invention.

INDUSTRIAL UTILITY

The disclosed invention improves quality and durability of capacitors inelectronic devices

1-40. (canceled)
 41. Capacitor precursor bodies prepared by the processof pressing a pellet of an anode in the shape of a regular prism,forming transition surfaces at edges of multiple surfaces, sintering thepellet, electrolyzing to form a dielectric oxide on the surface of thepellet and applying a slurry of a prepolymerized intrinsicallyconductive polymer to said oxidized pellet.
 42. Capacitor precursorbodies according to claim 44 wherein said forming transition surfaces atedges of multiple surfaces occurs during pressing.
 43. Capacitorprecursor bodies according to claim 44 wherein said forming transitionsurfaces at edges of multiple surfaces occurs after pressing. 44.Capacitor precursor bodies according to claim 44 wherein said sinteringis done prior to forming transition surfaces at edges of multiplesurfaces or after forming transition surfaces at edges of multiplesurfaces.
 45. Capacitor precursor bodies according to claim 44 whereinsaid transition surfaces are substantially chamfers.
 46. Capacitorprecursor bodies according to claim 44 wherein said transition surfacesare substantially curves.
 47. Capacitor precursor bodies according toclaim 44 having an anode lead inserted into said pellet before pressing.48. Capacitor precursor bodies according to claim 44 wherein saidintrinsically conductive polymer is built up on said pellet to athickness of at least about 0.25 micrometers.
 49. Capacitor precursorbodies according to claim 48 wherein said intrinsically conductivepolymer is built up on said pellet to a thickness of at least about 1.0micrometers.
 50. Capacitor precursor bodies according to claim 48wherein said intrinsically conductive polymer is built up on said pelletto a thickness of at least about 3 micrometers.
 51. Capacitor precursorbodies prepared by the process of pressing a pellet of a anode in theshape of a rectangular prism having transition surfaces at more than 5intersections of at least two surfaces, sintering the pellet,electrolyzing to form a dielectric oxide on the surface of the pelletand applying a slurry of a prepolymerized intrinsically conductivepolymer to said oxidized pellet.
 52. Capacitor precursor bodiesaccording to claim 51 wherein said intrinsically conductive polymer isbuilt up on said pellet to a thickness of at least about 0.25micrometers.
 53. Capacitor precursor bodies according to claim 52wherein said intrinsically conductive polymer is built up on said pelletto a thickness of at least about 1.0 micrometers.
 54. Capacitorprecursor bodies according to claim 52 wherein said intrinsicallyconductive polymer is built up on said pellet to a thickness of at leastabout 3 micrometers.
 55. Capacitor precursor bodies prepared by theprocess of pressing a pellet of an anode in the shape of a rectangularprism, forming transition surfaces at all intersections of at least twosurfaces, sintering the pellet, electrolyzing to form a dielectric oxideon the surface of the pellet and applying a slurry of a prepolymerizedintrinsically conductive polymer to said oxidized pellet.
 56. Capacitorprecursor bodies according to claim 55 wherein said forming transitionsurfaces at all intersections of at least two surfaces occurs duringpressing.
 57. Capacitor precursor bodies according to claim 55 whereinsaid forming transition surfaces at all intersections of at least twosurfaces occurs after pressing.
 58. Capacitor precursor bodies accordingto claim 55 wherein said sintering is done prior to forming transitionsurfaces or after forming transition surfaces.
 59. Capacitor precursorbodies according to claim 55 wherein said intrinsically conductivepolymer is built up on said pellet to a thickness of at least about 0.25micrometers.
 60. Capacitor precursor bodies according to claim 59wherein said intrinsically conductive polymer is built up on said pelletto a thickness of at least about 1.0 micrometers.
 61. Capacitorprecursor bodies according to claim 59 wherein said intrinsicallyconductive polymer is built up on said pellet to a thickness of at leastabout 3 micrometers.
 62. Capacitor precursor bodies prepared by theprocess of oxidizing a pellet of a valve in the shape of a rectangularprism having transition surfaces at more than three intersections ofthree surfaces.
 63. Capacitor precursor bodies according to claim 62further comprising an intrinsically conductive polymer wherein saidintrinsically conductive polymer is built up on said pellet to athickness of at least about 0.25 micrometers.
 64. Capacitor precursorbodies according to claim 63 wherein said intrinsically conductivepolymer is built up on said pellet to a thickness of at least about 1.0micrometers.
 65. Capacitor precursor bodies according to claim 63wherein said intrinsically conductive polymer is built up on said pelletto a thickness of at least about 3 micrometers.
 66. Capacitor precursorbodies prepared by the process of pressing a pellet of an anode in theshape of an obround prism wherein a prism shape is changed at least oneintersection of two surfaces to create transition surfaces, sinteringthe pellet, electrolyzing to form a dielectric oxide on the surface ofthe pellet and applying a slurry of a prepolymerized intrinsicallyconductive polymer to said oxidized pellet.
 67. Capacitor precursorbodies according to claim 66 wherein said prism shape is changed atleast one intersection of two surfaces to create transition surfacesduring pressing.
 68. Capacitor precursor bodies according to claim 66wherein said prism shape is changed at least one intersection of twosurfaces to create transition surfaces after pressing.
 69. Capacitorprecursor bodies according to claim 66 wherein said sintering is doneprior to said prism shape being changed at least one intersection of twosurfaces to create transition surfaces or after said prism shape beingchanged at least one intersection of two surfaces to create transitionsurfaces.
 70. Capacitor precursor bodies according to claim 66 whereinsaid intrinsically conductive polymer is built up on said pellet to athickness of at least about 0.25 micrometers.
 71. Capacitor precursorbodies according to claim 70 wherein said intrinsically conductivepolymer is built up on said pellet to a thickness of at least about 1.0micrometers.
 72. Capacitor precursor bodies according to claim 70wherein said intrinsically conductive polymer is built up on said pelletto a thickness of at least about 3 micrometers.
 73. Capacitor precursorbodies prepared by the process of pressing a pellet of an anode in theshape of a cylindrical prism wherein the edge of at least one flatsurface has been changed to create a transition surface, sintering thepellet, electrolyzing to form a dielectric oxide on the surface of thepellet and applying a slurry of a prepolymerized intrinsicallyconductive polymer to said oxidized pellet.
 74. Capacitor precursorbodies according to claim 73 wherein said edge of at least one flatsurface has been changed to create a transition surface during pressing.75. Capacitor precursor bodies according to claim 73 wherein said edgeof at least one flat surface has been changed to create a transitionsurface is after pressing.
 76. Capacitor precursor bodies according toclaim 73 wherein said sintering is done prior to edge of at least oneflat surface has been changed to create a transition surface or afteredge of at least one flat surface has been changed to create atransition surface.
 77. Capacitor precursor bodies according to claim 73wherein said intrinsically conductive polymer is built up on said pelletto a thickness of at least about 0.25 micrometers.
 78. Capacitorprecursor bodies according to claim 77 wherein said intrinsicallyconductive polymer is built up on said pellet to a thickness of at leastabout 1.0 micrometers.
 79. Capacitor precursor bodies according to claim78 wherein said intrinsically conductive polymer is built up on saidpellet to a thickness of at least about 3 micrometers.
 80. Capacitorprecursor bodies prepared by the process of pressing a pellet of ananode in the shape of a rectangular prism, forming transition surfacesat more than five intersections of two surfaces, sintering the pellet,electrolyzing to form a dielectric oxide on the surface of the pelletand applying a slurry of a prepolymerized intrinsically conductivepolymer to said oxidized pellet.
 81. Capacitor precursor bodiesaccording to claim 80 wherein said forming transition surfaces at morethan five intersections of two surfaces occurs during pressing. 82.Capacitor precursor bodies according to claim 80 wherein said formingtransition surfaces at more than five intersections of two surfacesoccurs after pressing.
 83. Capacitor precursor bodies according to claim80 wherein said sintering is done prior to forming transition surfacesat more than five intersections of two surfaces or after formingtransition surfaces at more than five intersections of two surfaces. 84.Capacitor precursor bodies according to claim 80 wherein saidintrinsically conductive polymer is built up on said pellet to athickness of at least about 0.25 micrometers.
 85. Capacitor precursorbodies according to claim 84 wherein said intrinsically conductivepolymer is built up on said pellet to a thickness of at least about 1.0micrometers.
 86. Capacitor precursor bodies according to claim 85wherein said intrinsically conductive polymer is built up on said pelletto a thickness of at least about 3 micrometers.
 87. Capacitor precursorbodies according to claim 51 wherein said transition surfaces are formedduring pressing.
 88. Capacitor precursor bodies according to claim 51wherein said transition surfaces are formed after pressing. 89.Capacitor precursor bodies according to claim 51 wherein said sinteringis done prior to forming transition surfaces or after forming transitionsurfaces.